Ni–Co layered double hydroxides (LDHs) have high theoretical capacities for energy storage by ion intercalation/release but suffer from the sluggish charge transport kinetics, hence are unsuitable for high-power supercapacitors nowadays. Herein, by intercalating the guest multi-carboxylic anions with straight-chain or conjugated-plane configurations, we have realized the sub-nanometer-scale fine regulation of the interlayer distance in Ni–Co LDHs for tuning the charge (ions and electrons) transport kinetics. With increasing the interlayer distance, the equivalent series resistance (R_ESR) shows the "inverted-volcano" evolution, which is first demonstrated for the anion-intercalated LDHs. With the smallest R_ESR, the LDH pillared by the conjugated 1,4-benzenedicarboxylic anion achieves the best matching between ion diffusion and electron transfer, and thus presents a high capacitance of 2115 F g⁻¹ at 1 A g⁻¹ and a record-high rate capability for the powder-like LDHs with the capacitance of 410 F g⁻¹ at an ultrahigh current density of 150 A g⁻¹. The corresponding hybrid supercapacitor coupled with activated carbon presents the high energy density of 11.2 Wh kg⁻¹ at the ultrahigh power density of 30.7 kW kg⁻¹, ranking at the top level for the supercapacitors based on the powder-like LDHs active materials. The minimal R_ESR from the "inverted-volcano" evolution could provide a feasible criterion to explore the high-rate LDH electrodes.

Ni-Co层状双氢氧化物（LDHs）具有高理论容量，可通过离子嵌入/释放进行能量存储，但受电荷传输动力学的影响，因此不适用于当今的大功率超级电容器。在这里，通过插入具有直链或共轭平面构型的客体多羧基阴离子，我们实现了Ni-Co LDHs中层间距离的亚纳米级精细调节，以调节电荷（离子和电子）的传输动力学。随着层间距离的增加，等效串联电阻（R _ESR）显示出“倒火山”的演变，这首先被阴离子嵌入的LDH证实。具有最小的R _ESR，由共轭1,4-苯二甲酸根阴离子担负的LDH达到了离子扩散和电子转移之间的最佳匹配，因此在1 A g ^-1下具有2115 F g ^-1的高电容，并具有创纪录的高倍率容量在150 A g ^-1的超高电流密度下，电容为410 F g ^-1的粉末状LDH 。相应的混合超级电容器与活性炭在30.7 kW kg ^-1的超高功率密度下表现出11.2 Wh kg ^-1的高能量密度，在基于粉末状LDH活性材料的超级电容器中排名最高。最小R _ESR 来自“倒火山”的演化可以为探索高速率LDH电极提供可行的标准。